Nonbenzenoid compounds



Patented Jan. 1, 1946 2,391,943 NONBENZENOID COMPOUNDS Lewis W. Butz,Beltsville, Md., assignor to Claude R. Wickard, as Secretary ofAgriculture of the United States of America, and his successors inoffice No Drawing. Original application December 12,

1942, Serial No. 468,795. Divided and this application July 10, 1945,Serial No. 604,290

(Granted under the act of March 3, 1883, as amended April 30, 1928; 3700. G. 757) 1 Claim.

This application is made under the act of March 3, 1883, as amended bythe act of April 30, 1928, and the invention herein described andclaimed, if patented, may be manufactured and used by or for theGovernment of the United materials.

States of America for governmental purposes without the payment to me ofany royalty thereon.

This application is a division of my copending application for PatentSerial No. 468,795, filed December 12, 1942.

My invention relates to non-benzenoid fused polycyclic organic compoundsand to processes for preparing them.

I have found that organic compounds belonging to the class of1,5-diene-3-ynes, i. e., compounds containing the atomic grouping reactwith two moles of dienophilic compounds containing the atomic groupingsuch as, maleic anhydride, methyl fumarate, ethyl fumarate, and othermaleates and fumarates including substituted compounds, to form stableaddition products which contain two carbon rings more than are containedin the dieneyne employed. The reaction is carried out in the absence ofany solvent and at a temperature of 130 C. to 175 C. The molecularweight of these products is equal to the sum of the molecular weight ofthe dieneyne employed and twice the molecular weight of the dienophiliccompound used.

Thus the dieneyne, cyclohexenylcyclopentenylacetylene reacts readilywith maleic anhydride. By this reaction, there is formed a compoundcontaining four rings of carbon atoms having substantially thestructure:

This is a non-benzenoid steroid. It possesses the seventeen-carbonfour-ring skeleton common to all the steroids which have been found inorganic Furthermore, it is a steroid containing only hydrogenated ringsand one novel feature of the process is its capacity to yield polycycliccompounds lacking any aromatic (benzenoid) ring.

All known processes for the synthesis of steroids relate to thepreparation of benzenoid steroids. But the majority of the naturallyoccurring steroids, among them the therapeutically important malehormones, adrenocortical hormones, and progesterone are non-benzenoid.

My process makes available, for the first time, by synthesis, steroidsof the non-benzenoid type, as well as non-steroid types of polycycliccompounds, which are useful as intermediates in the synthesis oftherapeutic compounds,

The following example for .the preparation of trans 6,7 trans 11,12tetracarbomethoxy- 8(14),9-chrysitadiene will illustrate my inventionmore fully.

One molecular proportion of dicyclohexenylacetylene and two molecularproportions of methyl fumarate were heated under nitrogen in a sealedtube at C. for 24 hours, and then subjected to vacuum distillation,which resulted in a viscous, amber residue. This residue was"crystallized from methanol, yielding the product:

0 o 0 OH;

structure:

0 o 0 on:

OHaOOG I

